Tris(cyanoethoxymethyl) benzenes



United States Patent 3,193,371 TRES(CYAN@ETHGXYMETHYDBENZENES Raymond L. Wayirevv, Summit, Ni, and Earl P.

Williams, Pen Argyl, Pa, assignors to General Aniline 8; Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Get. 5, 1961, er. No. 143,039 17 Claims. (Cl. T l-23) This invention relates to novel benzene derivatives. More particularly, it relates to novel substituted benzenes containing nitrile groups in the substituent groups.

Specifically, this invention relates to tris(cyanoethoxymethyl)benzeues, to a method for preparing these novel compounds, and to certain uses hereinafter described.

Compounds containing nitrile groups generally have toxic properties. However, they are usually non-specific in their action and are, therefore, of little value especially as pesticides, because of their deleterious effect on the environment as a whole. Accordingly, While such compounds might readily kill various pests, they are too dangerous to use because of their toxic effects on desirable plant and animal life.

While many good insecticides are available no effective nematocide has up to the present been discovered which is not only an efiicient toxicant for nematodes, but which will not damage the crop plants which it is desired to protect against these pests. Many nematocides now in use sterilize the soil or are either nonselective herbicides or damage plant life to one or another significant degree.

Since nematodes cause heavy losses to agriculture amounting to several hundred million dollars annually, it will be readily apparent that a good nematocide which will be effective only against the pests, but which will cause no damage to plant life or which will be toxic only to undesired plants, such as weeds, would be of great benefit to the farmers.

A primary object of this invention is to provide novel nitrile-containing compounds. Another object is to provide a novel method for their preparation. A further object is to provide a number of novel nitrile-containing benzene derivatives which are efiective pesticides. A still further object is to provide a number of novel nitrilecontaining benzene derivatives which are not only effective pesticides, but which are also good herbicides. Other Objects will be apparent to those skilled in the art from the description of the invention which follows.

In general, it has been discovered that when certain methylol-substituted benzene-s are reacted with acrylonitrile there are obtained the corresponding cyanoethoxyethyl-substituted bcnzenes. More specifically, it has been discovered that when 1,2,4- and 1,3,5-trimethylol'oenzene are reacted with three moles of acrylontrile there are obtained the corresponding tris(cyanoethoxymethyl)benzenes.

These compounds are not only effective nematocides but are also good preand post-emergence herbicides which exhibit a selective toxicity to weeds without damaging crop plants, such as corn, soybeans, Wheat, and cotton.

The starting materials used in the present invention namely, 1,2,4- and 1,3,5-trimethylolbenzene can be prepared by the trimerization of propargyl alcohol. The

two isomers are obtained as a mixture which may be separated, if desired, or used directly. As will be shown below, the mixture of tris(cyanoethoxymethyl)benzenes, obtained by reacting one mole of the unseparated mixture with 3 moles of acrylonitrile, is itself extremely effective.

In addition, 1,3,5-trirnethylolbenzene can itself be prepared according to the disclosure in Beilstein, vol. Vi, page 1127.

The invention is illustrated by the following examples:

EXAMPLE 1.PREPARATION OF TRlS(CYANO- ETHOXYIflETHYL) BE-NZENES Into a one-liter flask provided with a stirrer, thermometer, dropping funnel, and a condenser equipped for vacuum take-off were charged 168.2 grams (1 mole) of trimerized propargyl alcohol comprising essentially a mixture of 1,2,4- and 1,3,5-trimethylolbenzene and 2 grams of 40% sodium hydroxide solution. The mixture was stirred well while the temperature was raised to C. at 30 mm. pressure. The vacuum was then released and heating continued until the temperature rose to C. at this time the dropwise addition of 160 grams (3 moles) of acrylonitrile Was begun 1% hours being required to add the complete amount. The temperature during the addition of the acrylonitrile was maintained at 85-95 C. After all of the acrylonitrile had been added, the reaction mixture was held at a temperature of 85-95 C. for two hours longer, then cooled to 65 C., and the sodium hydroxide catalyst neutralized by the addition of 1.2 grams of glacial acetic acid. A small amount of residual salt Was filtered off.

The product was then Washed with methanol and dried by distilling off the low-boiling components at C and at a pressure of 30 mm.

Analysis of the product layer gave 11.8% N (calc.: 12.8% N) and an 0H number equivalent to 42 mg. of KOH per gram. This corresponds to a 91% conversion of the trimethylclbenzene.

Toxicant compositions containing the above-produced tris(cyanoethoxymethyl)benzenes can be formulated as dispersions in either liquid or solid carriers. Thus the compounds can be employed as solutions in suitable inert solvents which do not react with the toxicants and which preferably do not have any harmful effects on plant life. Acetone is one such suitable solvent. Solutions prepared in this manner are effective in concentrations of about from 0.001 to 20% by weight. Preferred concentrations range about from 1 to 15%.

The toxicant can also be prepared sion when it is desired to drench the benches or the like.

Where it is desired to apply the toxicant as a dry formulation, it can be prepared as a dusting composition, using pumice, talc, or clay as solid carriers.

One extremely satisfactory method according to the present invention is to inject the nematocide into the soil. This is done by filling holes or other Openings in the soil with the desired amounts of the toxicant.

EXAMPLE 2.NEMATOCIDAL ACTIVITY A brei of tomato roots, infested with root knot nematodes, Melz'odogyne incognito was prepared by cutting as an aqueous emulsoil, as in greenhouse roots of infested tomato plants into quarter inch lengths and then further macerating in a Waring Blendor for one minute.

Duplicate 100 gram samples of dry sand were mixed with gram portions of the above described brei. The sand and brei were mechanically mixed by shaking for preemergence effects of tris(cyanoethoxymethyl)benzene.

' A similar series of tests were also made to determine the post-emergence effects of the compounds. These were carried out by permitting the seeds to emerge before treatment.

a one minute in a closed Mason jar and then transferred To provide a standard for comparison, a parallel series to 2% inch clay pots. At this time, 50 mg. of the toxiof experiments was performed with a known nematocide, cant was added to the mixture in each pot. The pots 3-(p-chlorophenyl-l,l-dimethylurea (CMU), applied at were then individually wrapped in Saran and allowed to the rate of 1 pound per acre. t d for 24 hours The results of the pre-emergence tests are given in At the end of 24 hours the contents of each pot were Table 2, below: transferred to stainless steel cylindrical screens each ap- Table 2 proximately 2 /2 inches high'and 3 /2 inches in diameter.

Each screen was then placed in the bottom halfof a 9 weeds cm. petri dish containing 25 ml. of water and covered Chemical 7 with the petri dish cover. After a short time an addi- Broad leaf Grasses tional 10 ml. of distilled water was added to each plate V SO 1111211111566 Water WaS available in the dish. After 24 Tris(cyanoethoxymethyDben- Very light sta.ud Light stand. hours, microscope counts were made of the living nemafi fi m 1007 (no Stud) 1007 (no stand) todes which had migrated through the screen into the H a 0 petri dish. At least 10 fields were read, or 150 nema v 1N0 miurynoted tocom, Soybean, cotton, and wheat todes counted per dish. Duplicate tests were made for Heavy injury noted to corn,scyhcan, cotton, and wheat. Check Pll The m are given in Table e The results of the post-emergence tests are given in Table 1 Table 3, below:

a 25 Table 3 Nematodes in 10 fields Weeds Compound Chemical Living w o Broad leaf Grasses Tris(cyanoethoxymethyhbeiizeues 1 36 Tris(cyanoethoxymethyDben- Verylightstaud Medium stand. Blank I 80 zene mixture OMU 2 100% (no staud) 100% (no stand).

The compounds of the present invention were also tested as herbicides for their efiectiveness i d 35 gg g g llury noted to corn, soybean, cotton, and wheat which were post-emergence weed control and for their toxicity to Heav injury noted to corn, soybean, cotton and wheat. desirable field crops. The test plants included broadleaf It i t b der tood that the foregoing detailed d Weeds and grasses, W611 as Seeds of 00m, Soybeans, scription is given merely by way of illustration and that 7 Wheat, d cDUOII- Soybean W33 315-0 used n the many variations may be made therein Without depart-.

P t m in the 'lfi-foliate eing from the spirit of this invention.

7 What iS claimed is; u

1. A compound selected from the group consisting of F one Square foot a were fined wlth 9 1,2,4 tris(cyanoethoxymethyl)benzene, 1,3,5 tris(cyanosoil m xture to a depth of 5 inches and packed solid with ethoxymethynbenzene and mixtures ,thereoi a firming board. C otton, corn, soybeans, and wheat seeds 2, 1,2,4-tris(cyanoethoxymethyl)benzene. were then planted in rows in separate flats at the rate of 135 triS(cyanoethoxymethyl)benzerm 15 cotton, corn, and soybean seeds and 3 cc. of wheat Amixture of 1244118(cyanoethoxymethyl)benzene per flat. One half a level teaspoon of mixed weed seeds, and 1,3,54ris(cyanoethoxymethyl)benzene. were scattered uniformly over the surface of the soil in method for controlling nematode infestations each layer of 5011 mch thlck added to cove? the which comprises contacting nematodes with an active seeds P then dh flats were watered hght' substance selected from the group consisting of 1,2,4-tristo Induce germmatlon- (cyanoethoxymethyl)benzene, 1,3,5 tris(cyanoethoxy- After the flats had been prepared as ust described, a methynbenzene and, mixtums thereoi suflicient amount of the mixture of isomers of tris(cyano- A method for controlling nematode infestations eihQxymethynbenzqnes Prepared Example to which comprises contacting nematodes with a mixture of vide exactly the equivalent of 16 pounds per acre for each 1,2,4 tris(cyanoethoxymethyl)benzene and 1 3 5 flat (1 square foot) was dissolved in 3 ml. of acetone per. (cyanoethoxymethyl)benzene flat, 3 m1. of 1% Igepal CO-630 a commercial wetti g 7, A method for controlling nematode infestations agent P flat added acetone 501119101: and then which comprises contacting nematode-infested soil with enough water added to provld? fi a v lu of not less a mixture of 1,2,4-tris(cyanoethoxymethyl)benzene and than 15 per flat (200 2 Per acre)? 1,3,5-tris(cyanoethoxymethyl)benzene.

h flat was spfaycd uniformly at a Pressure 2 8. A method for controlling nematode infestations Pound's'per square Inch w 15 mL of the composltlon which comprises contacting the roots of nematode- PrePared as above -l f and Pihen cultured under infested plants with a mixture of 1,2,4-tris(cyanoethoxystargle alrd greenhouse conditions. Water was added as methynbenzene and 1,35 tris(cyanoethoxymethynbem nee zene.

T seeds thus treated were permlited to grow for 9. A method for controlling weeds, which comprises aboui four weeks- At the end of that time: the flatswere applying to the soil of weed-infested areas an active subexamined for weed control of both broad leaf weeds and stance selgcted f the group consisting of 11 4 asses. (cyanoethoxymethyl)benzene, 1,3,5 tris(cyanoethoxy- Germination counts were made of crop emergence and h nb d mixtures th f inhibition PP- of growth and y other 11111151131 10. A method for controlling weeds which comprises effects were noted. Weed control was rated in terms of applying to the soil of weed-infested areas a mixture of heavy, medium, light, or very light stands. 1,2,5-tris(cyanoethoxymethyl)benzene and 1,3,5-tris(cy- The above described tests were run to determine the anoethoxymethyhbenzene.

11. A method for controlling weed infestations which comprises applying a mixture of 1,2,4-tris(cyanoethoxymethy1)benzene and 1,3,5-tris(cyanoethoxymethyl)ben zene to weed seed-infested soil prior to emergence.

12. A method for controlling weed infestations which comprises applying a mixture of 1,2,4-tris(cyanoethoxy methyl)benzene and 1,3,5 -tris(cyanoethoxymethyl)benzene to growing weeds.

13. A nematocidal and herbicidal composition consisting essentially of a substance selected from the group consisting of 1,2,4-tris(cyanoethoxymethyl)benzene, 1,3,5- trist'cyanoethoxymethyl)benzene, and mixtures thereof and a carrier therefor.

14. The nematocidal and herbicidal composition according to claim 13 wherein said carrier is a solid.

15. The nematocidal and herbicidal compositions according to claim 13 wherein said carrier is a liquid.

16. The nematocidal and herbicidal compositions according to claim 13 wherein the amount of said active substance presence is in the range of from about 0.001 to about 20% by weight.

17. A nematocidal and herbicidal composition comprising an aqueous dispersion of a mixture of 1,2,4-tris- (cyanoethoxymethyl)benzene and 1,3,5-tris(cyanoethoxymethyl)benzene, said dispersion containing said mixture in an amount in the range of from about 0.001 to about 20% by weight.

References Qited by the Examiner UNITED STATES PATENTS 2,401,607 6/46 Bruson 260465.6 2,818,422 12/ 57 Heininger 260-465 2,819,197 1/58 Santmyer et al 167-13 2,819,291 1/ 58 Heininger 260465 3,007,786 11/61 H'amm et a1. 712.3 3,007,788 11/61 Josephs 71-2.3 3,021,258 2/62 Haynes 1673O 3,085,930 4/63 Braunholtz et a1. 167l3 3,108,038 10/63 Fielding l6730 FOREIGN PATENTS 811,350 8/51 Germany.

OTHER REFERENCES Utermohlen: J.A.C.S., vol. 67, 1945, pages 1505-06.

JULIAN S. LEVITT, Primary Examiner.

M. A. BRINDISI, Examiner. 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1,2,4-TRIS(CYANOETHOXYMETHYL)BENZENE, 1,3,5-TRIS(CYANOETHOXYMETHYL)BENZENE, AND MIXTURES THEREOF.
 5. A METHOD FOR CONTROLLING NEMATODE INFESTATIONS WHICH COMPRISES CONTACTING NEMATODES WITH AN ACTIVE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF 1,2,4-TRIS(CYANOETHOXYMETHYL)BENZENE, 1,3,5-TRIS(CYANOETHOXYMETHYL)BENZENE, AND MIXTURES THEREOF. 